Triazine fluorescent agents



Patented Nov. 24, 1953 UNITED STATES PATENT OFFICE TRIAZINE FLUORESCENT AGENTS William W. Williams, Easton, Pa., and William E.

Wallace, Rensselaer, N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.

This invention relates to novel fluorescent agents derived from 4,4-diamino-2,2-stilbene disulfonic acid.

We have found that valuable intermediates for producing fluorescent agents may be obtained by (CHaOGH:CH2OR) Formula I I wherein Y represents a member of the group consisting of hydrogen and methyl and n represents the integers 1 or 2 and R represents hydrogen, hydroxyethyl or lower alkylmethyl.

There is thus obtained a novel intermediate of the present invention which may be represented by the following formula SOIH Formula II wherein n, Y and. R are as defined above.

By condensation of this novel intermediate with at least two molecular proportions of an amine or organic hydroxy compound, valuable fluorescent agents are obtained. In case an amine is to be condensed with this novel intermediate, it may be selected from the group consisting of primary and secondary lower (1-4 carbon atoms) alkyl amines (e. g. dimethyl amine, diethyl amine, etc.), primary and secondary lower (1-2 carbon atoms) alkylol amines (e. g. monoor di-ethanolamine) and primary and second- Application January 23, 1952, Serial No. 267,921

. 6Claims. ((1260-2471) ary aryl amines (e. g., aniline, N -cnethylor N-ethyl-aniline, toluidine, anisidine) and heterocyclic amines (e. g., pyrimidine, tetrazole, benzethiazole, thiazole, pyridine, morpholine, thiomorpholine). If an organic hydroxy compound is to be condensed with this novel intermediate, it may be'selected from the group consisting of alkanols, preferably ll carbon atoms (e. g. methanol, ethanol, propanol or butanol) aryl hydroxy compounds (e. g. phenol, monomethylor monoethyl-ethers of resorcinol, hydroquinone or pyrocatechol etc.) and heterocyclic hydroxy col pounds (e. g., hydroxy quinclines, hydroxy quinaldines, etc.).

The thus obtained fluorescent agents, when in 'oorporated, either in the form of the free sulfonic acids or ammonium or alkali metal salts thereof, into paper or other wrapping material improve the whiteness as well as protect the contents from the action of ultraviolet light. They are useful in improving the whiteness of paints; when applied to fabrics by methods well known in the art, the whiteness is remarkably improved. The white background of photographic prints and diazotype prints can be improved by incorporating some of the material into the coating formulations. By addition of some of the materials to discharge pastes, the whites which are obtained upon discharge are remarkably whiter than discharges which-are made in the absence of this material. If small amounts of these materials are used in soaps or other detergents, fabrics which are washed using these formulations will be much whiter in the case of whites and brighter in the case of colors than fabrics which are washed with ordinary soaps or detergents. These materials may be used in bleaching processes for various fibers. In such cases, the amount of bleach necessary is materially reduced.

The novel intermediate for and the novel fluorescent agents of the present invention and their method of preparation may be most readily described by consideration of specific examples thereof:

EXAMPLE I Thirty-seven parts (0.2 mole) of cyanuric chloride are dissolved in parts of acetone and poured into a mixture of ice and water. During the suspension in ice water, the temperature of the aqueous suspension should not rise above 5 C. Thirty-seven parts (0.1 mole) of 4,4cliaminostilbene-2,2'-disulfonic acid are dissolved in parts of water with the addition of enough sodium carbonate to give a neutral solution. This solution is added slowly to the cyanuric chloride suspension and at the same time a solution of sodium carbonate is added in order to keep the mixture from becoming too acid. The tempera-- ture should not rise above 5 C. during this con densation. The condensation is complete when a sample of the-reaction mixture whichhas been acidified and treated with sodium nitrite does not develop color when treated with an alkaline solution of R salt.

When the condensation is complete, a solution of 51 parts (or two moles) of 2,2-(4-amino-2,6- tolylenedimethoxy) diethanol HOCHzCHzOCHr CHaOOHzCHaO'H NH: Formula 111 is added and immediately afterward a solution of 160 parts of anhydrous sodium acetate in 400 parts of water is added. The mixture is allowed to warm to room temperature and may be heated to 35-40 C. if necessary to complete the condensation. There is thus-obtained a :novel intermediate of the formula given'above in which Y is methyl, R is hydrogen and n is 2.

When this secondary condensation is complete, 30 parts (0.3 mole or approximately 50% excess) of diethanolamine .is added and the pH is increased to 8-8.5 with sodium carbonate solution. Then the mixture is heated slowly to 90 C. and maintained at that temperature .for 3 hours. The mixture is then cooled and the product is isolated in the usual manner.

The material which is obtained is tan in color and moderately soluble in water but very sparingly soluble in acetone, alcohol, ether, etc. It corresponds to the .formula:

HO CHaU H:OCH2- CHI'OEHaCHaOLH NH I at i I(CH2C H1011):

Formula IV When this material is incorporated into discharge pastes and applied to fabrics, the whites thus obtained are remarkably whiter than those obtained using ordinarydischarge pastes. When this material is applied .to fabrics of cellulose. wool or nylon by methods well known in the art, the white appearance of theiiber is thereby much improved. If small amounts of :this substance are added to soaps or other detergents and the resulting mixture is used to wash fabrics of cellulose, wool, or nylon, the white materials thus washed are extraordinarily whiter in appearance and colored materials are brighter than similar materials which are washed using ordinary soaps or detergents.

The detailed procedure of the foregoing example has been employed to produce a number of the novel products of the present invention.

These novel products may .be represented by the following general formula:

(CHr-OCHaCHaORh Formula VI and Formula VII in which Y represents hydrogen or methyl, R represents ethanol or methyl, n represents 1 or 2, M represents hydrogen or ammonium or alkali metal and R1 may represent hydrogen or lower (1-4 carbon atoms) alkyl group such as and R2 .may represent one of the alkyl or alkylol groups .of the type given above or. aryl, such as phenyl, methoxy phenyl or heterocyclics such as pyrimidine, tetrazole, benzothiazole, pyridino, etc. and finally the group may represent cyclic residues such as pyrimidine, morpholino, thiomorpholine.

Since other typical fluorescent agents, which had properties substantially parallel to the properties of the product of Example I of this inven- ,tion, have been produced by duplicating the detailed procedure described above in Example I while replacing in the diethanolamine employed 'in Example I with corresponding molecular quantities of other amines or hydroxy compounds and/or using in place of the 2,2-4-amino-2,6- toluenedimethoxy diethanol corresponding molecular quantities of other amino benzyl ethers of the type indicated; the complete details of their preparation are not given but (1) the particular amino Ibenzyl ether and/or (2) the particemployed. In each case the same molar amounts 5 compound).

of reactants were used as in Example I (1. e., 0.2 mole cyanurio chloride, 0.1 mole 4,4-diamino- 2,2-sti1bene disulfonic acid, 0.2 mole amino benzyl ether and 0.3 mole of amine or organic hydroxy Table I 1 A 2 13 Ex ple Amino benzyi S ubstituent A Amine or organic hy- Substituent B ether employed In formula V droxy compound used in formula V H NH 1: /CH: /C H:

I I HN N\ CH: C H;

HO CHzCHzO 0111- CEO CHaCHOfl HOCHaOHaOOH CHaOCHaOETaOH III HOCBzCHaOGHa OHzOCHnCHzOH IV NH:

HOCHICHaOCH: CHaOCHzCHnOH V NH HOCH:CH:OCH: -CHaOCHaCHaOH HOCHaCHqOOH: CHQOCHQCHQOH HOCHICHjOCHZ -CH2OCHICH2OH VIII HOOHzCHaOCH: CHaOCHaCHzOH HOCHzCHzOCH: CHIOCHQCHiOH HOCHaOHaOCH OHzOOHaCHaOH 1 NH HO CH1CH:OCH:Q-CH:OCH:CH2OH 0 HI I HOGHaOHzOCHa-QCHQOOHKJBHOH HOCHsCHaOCHr- CHQOCHaCHaOH HOCHaOHaOCH CHaOCHaOHaOH HOCHICHIOCH OHIO CHaCHaOH l NH HOCHaCHiOCH CHaOCHaCHzOH mN-Ooom mooQoH 1 A i 2 B Example Amino benzyl Substituent A Amino or organic hy- Substituent B ether employed in formula V droxy compound used in formula V XIX NH, I

NH HzNOOCHs JEN-O-OOH; OCH2OCHICH2OH CHIOCHICHIOH CH3 (5H: XX I'VE; --NH CHaCHaOH CHECHQOH HN -N\ 011,011,011 cmomou CHKOCHqOHMOCH; -CH;(OOH:CH:)|0CH XXI BITE: NH CH: CH:

HN N CHI CH; -CHa(OCHzCHa)zOCHg CH|(OCH2CH:)1OCH XXII Hi1? HN- CHiCHaOH CHiOHiOH HN N\ CHICHgOH CHiCHnOH CHQOCHEOHOCHIGHIOH 'CHOCHICHOCHSOHIOH XXIII H:N OCHzOCHaCHzOCHaOHlOH CH:O OHgCHaO CHaCHzOH ENG-0 on,

HN-OOCH;

It will be apparent that the products obtained in the above examples were produced in the form of their sodium salts. However, the free acids, if desired, may be obtained by the acidification of the thus obtained sodium salts and other salts such as ammonium or potassium salts produced therefrom. by neutralization of the free acids.

It will also be apparent that the potassium salts may be obtained directly by replacing the sodium carbonate and acetate in the above examples with potassium carbonate and acetate, respectively.

Where spirit solubility is desired the amine salts such as dicyclohexyl amine salts may be produced by neutralization of the free acids.

We claim:

1. Flourescent agents which in the form of th free acid have the formula 1 sons X wherein R represents a member of the group consisting of hydrogen, hydroxy alkyl and lower alkyl, n represents one of the integers 1 and 2, and X represents a member of the group consisting of halogen, secondary dialkylamino, second- HO CHrCH OCH 3. Fluorescent agents which in the form of the free acid have the formula HOOHaCHaOCHI CHzOCHaCHzOH SOZH 4. Fluorescent agents which in the form of the free acid have the formula (IJHa HOOHzCHzOCHa- CHzOCHzOBzOH 5. Fluorescent agents which in the form of the free acid have the formula HOCHnCEhOCHz- CH2OCH:CH=OH -HO C-HzOHzOOH:

6. Fluorescent agents which in the form of the free acid have the formula CHaOCHzCHzOH WILLIAM W. WILLIAMS. WILLIAM E. WALLACE.

References Cited 'in the file Of this 'bate'nt UNITED STATES PATENTS 

1. FLUORESCENT AGENTS WHICH IN THE FORM OF THE FREE ACID HAVE THE FORMULA 